Process for the production of halogen-containing dioxene- and alpha-keto-oxetane derivatives



United States Patent many No Drawing. Filed Nov. 16, 1966, Ser. No. 594,699

Claims priority, application Germany, July 30, 1966, St 25,703 Int. Cl. B01j 1/10 US. Cl. 204-158 10 Claims ABSTRACT OF THE DISCLOSURE Process of preparing halogen containing dioxeneand u-keto-oxetane derivatives having the formulae:

wherein R and R each represent one of hydrogen, alkyl, aryl and aralkyl and wherein R and K, may be joined together with the carbon atoms to which they are attached to form an unsaturated monocyclic or polycyclic ring system, with the proviso that only one of R and R can simultaneously be hydrogen, and R R R and R each represent one of hydrogen, halogen, alkyl, aryl and aralkyl and wherein any two of R -R may .be joined together with the carbon atoms to which they are attached to form a monocyclic or polycyclic ring system, with the proviso that at least one of Ra-Rg is halogen, which comprises reacting a dicarbonyl compound having the formula:

with an olefinically unsaturated compound having the formula:

Rs B4 with light which will not be absorbed by the reaction product.

This invention relates to a process for the production of halogen-containing dioxeneand a-keto-oxetane derivatives.

It is known that oxetanes are obtained in good yields by reacting a perfluorinated monocarbonyl compound with ethylene, vinyl fluoride or vinylidene fluoride under the action of actinic radiation. For example, two' isomeric oxetanes of the formulae or, or, 5 cry-J: --o er -i: --o

Ha -63H]? JJHFHJJH2 are obtained as the reaction product of-hexafluoroacetone O Y 10 g and vinyl fluoride (CH =CHF). It is also known that the photoreaction of phenanthrenequinone-9,10 with benzocyclic olefins may proceed with both 1,2-addition to only one carbonyl group to form alpha ketooxetanes and 1,4-addition to both carbonyl groups to form phenanthredioxenes.

However, it is also known that if olefins carrying a halogen atom at one of the carbon atoms from which the double bond extends are used, this photoreaction gives dioxynes rather than dioxenes.

For example, phenanthrene quinone and chlorostilbene give a phenanthro[9,10-b] [l,4]-dioxyne when irradiated with solar light for six months in a benzene solution. This reaction can be represented by the following equation:

While the assumption has been made so far that the reaction shown above would proceed via an intermediate product of the formula O 01 l (l Ph I (J-Ph o H it was not possible up to the present to intercept this intermediate compound.

It is an object of the present invention to provide a process which permits the production of halogen-substituted dioxeneand alpha keto-oxetanes in a simple manner. Accordingly, the present invention relates to a process for the production of halogen-containing 'dioxeneand alpha keto-oxetane derivatives of the general formulae 0 s Iii-(i=0 R R1-C/ \(5-R4 R2- B, and R2- "R5 R5 0 R5 I! Patented May 12, 1970 rein R and R, are hydrogen, substituted or unsub- 16d alkyl, cycloalkyl, aryl, aralkyl or heteroyl and be joined to form a saturated or unsaturated, subted or unsubstituted ring and R R R and R, are gen, substituted or unsubstituted alkyl, cycloalkyl, aralkyl or heteroyl, at least one of the groups R R and R, being halogen'and two of the radicals R R and R may be joined to form a saturated unsaturated, substituted or unsubstituted ring, the css comprising reacting a dicarbonyl compound of the :ral formula rein R and R, are as defined above with an olefinir unsaturated compound of the general formula R Rt - Ih Rl .ein R R R and R are as defined above while liating light into the prebands of the carbonyl com- 1d, said irradiation being efiected through a light which does not transmit light which would be abed by the product being formed.

has been found in accordance with the invention the compounds prepared by the process of the inion are generally extremely sensitive to light having lengths of below 370 'millimicrons and undergo mposition with monomolecular cleavage of two subents, e.g. with formation of hydrohalic acid. This rising fact which could not be predicted is the reawhy it was previously impossible to isolate the interiate compound assumed to exist when reacting lanthreneq'uinone with chlorostilbene. hen carrying out the process of the invention, a soluof the components is irradiated in such a manner only the first absorption band of the 1,2-dicarbonyl pound is stimulated, e.g. with light of wave lengths as 400 millimicrons. When using usual light sources as mercury high pressure burners, xenon high presburners or solar light, it is necessary, therefore, to a light filter which prevents irradiation with light :h is absorbed by the adduct 'being formed. An examf a suitable light filter is a WG glass of Glaswerke theimvwhich does not transmit light of wave lengths a 370 millimicrons. Of course, it is possible to use sources which directly emit light of the wave length ed so that a light filter is not necessary for these sources. re use of a specific solvent is not critical, preferred g aromatic solvents, especially benzene. he formation of the reaction products (I) and (II) be accompanied by the formation of the by-products P and (IV) having the following general formulae:

:h are as low as possible although the reaction tem- Examples of 1,2-dicarbonyl compounds which may be used as the starting materials for the process of the invention include Examples of halogen-containing olefins which may be used as starting'materials in the process of the invention include compounds of the formulae ArCH=CHalEr "'I b wherein Ar is aryl and Hal is halogen.

As is obvious from the above statements, the compounds falling under the invention are formed under the action of longwave light while they undergo decomposition when irradiated with light having a wave length of, for example, below 370 miilimicrons.

The compounds prepared by the process of the invention owe to the finding of this fact not only their preparation but also their uses. Thus, the compounds prepared;

Photoaddition of phenanthrenequinone-(9,l0) to vinyl chloride This experiment gives the following products:

' (1) C I-1 C1 (305.2). CalcL: C, 62.96; H, 3.30; CI,

23.24. Found: C, 63.56; H, 3.39; CI, 22.58. Molecular H weight, 303 (osmotic pressure method in benzene). 1 i 5 1 o 2 0 .11 .01.0 (305.2). 0616.: c, 62.96; H, 3.30; ct, H 0 23.24. Found: 0, 63.33; H, 3.18; 01, 21.93. mm 304 (osmotic pressure method in benzene).

(Iv) Y Vinyl chloride was introduced into a suspension of phenanthrenequinone (1.04 g., 5 mmoles) in benzene (70 ml.) at 15 C. until the suspension was saturated (increase in volume to 110 ml.). After irradiation for 1.6 hours with light having a wave length of above 385 millimierons at about 10 C., the phenanthrenequinone was dissolved and the solution was only weakly yellow. The solvent was removed and the residue was mixed with 30 EXAMPLE 3 g ff f gfi ififfgfifl,fliijgg gifij 2 2:6 9: 2? Photoaddition of phe'nanthrenequinone to2-chloroindem melting point. Evaporation of the ether and subsequent A solution is prepared from 1.04 g. (5 millimoles) o: chromatography on Florisil with petroleum ether (60 to phenanthrenequinone and 3.01 g. (20 millimoles) of 2 80 C.) gave first 420 mg. of the product of the Formula chloroindene in 100 ml. of benzene. This solution is it I and then, with petroleum ether/cyclohexane, additional radiated for 1 hour with the use of a filter glass whicl 220 mg. of (III) (a total of 410 mg.). The products (11) does not transmit light of wave lengths above 27,000/cm and (IV) could only be eluated with benzene/chloroform. After the irradiation, the benzene is distilled ofi and th After boiling with 15-20 ml. of ethanol, 22 mg. of (IV) residue obtained is subjected to chromatography 01 remained undissolved. 280 milligrams of (H) could be Florisil. Elution with oyclohexane/benzene gives 140 mg recovered from the solution. After recrystallization, the ofthe product of'the Formula 1 which after recrystalliza substances were colorless. tion from a mixture of ethanol and benzene has a melt ADDUCTS (I) TO (IV) PREPARED Adduct Analysis of ield Empirical formula, formula percent Becrystallized rommelting point, 0. Molecular Weight 1 Y C H 01 I 31 Petroleum ether (100- 0101110101, 168-170 0--.. Calculated, 270.7; found, 71.00 4.10 13.08 140 c.). 5 71.47 3. 97 12.73 11 21 Ethanol (315110.101,144-146 0.... Calculated, 270.1; found, 71.00 4.10 13.08 271. 70. 95 4. 00 12. 90 III 37 Xylene 010131304, MS-349 C Calaulated,442.5; found, :1; 2.1. 2 1v 2 Dimethylformamlde 010111.01, 27s-279 o3.--" 0510111815011, 442.5; found, 81144 1101111111 1 Osmotic pressure method. 2 Above 190 0., decomposition with the color turning to green.

' With decomposition.

EXAMPLE 2 ing point of 213-215 F. Elution with benzene/chlorc P form gives 740 mg. of the product (2) which after r hotoaddl on of gg vmyhdene crysgalhzation from dioxane/water has a melting poir of 1 9-172 C. A olunon f a; ofrhenanthreneqwnone a 20 1 0 11 .0 322.4 Molecular weight, 318 (osmoti ml. of vinylidene chloride in 150 ml. of benzene is pre- Pressure h d i b pared and irradiated for 6 hours with the use of a filter glass which does not transmit light of wave lengths above 27,000/cm. The benzene is then distilled oil and the residue subjected to chromatography on Florisil. Elution with petroleum ether gives 220 mg. of the compound referred to hereafter as (1) and having a melting point of 131-133 C. The petroleum ether used has a boiling 0 I point of between 100 and 140 C. Subsequent elution l with benzene/chloroform gives 1.1 g. of an impure prod- J\ not of the Formula 2 shown below. Recrystallization 0 from petroleum ether (boiling range, to C.) gives yellowish crystals having a melting point of 104 to 107 C. 75

What is claimed is: Process of preparing halogen containing dioxenea-keto-oxetane derivatives having the formulae:

rein R and R, each represent one of hydrogen, alkyl, and aralkyl and wherein R and R may be joined ther with the carbon atoms to which they are attached an an unsaturated'monocyclic or polycyclic ring syswith the proviso that only one of R and R, can lltaneously be hydrogen, and R R R and R, each esent one of hydrogen, halogen, alkyl, aryl and araland wherein any two of RrR may be joined together the carbon atoms to which they are attached to form onocyclic or polycyclic ring system, with the proviso at least one of R R is halogen, which comprises ting a dicarbonyl compound having the formula:

an olefinically unsaturated compound having the rule:

R I \E/ Process according to claim 1 wherein-said irradiais efiected using a light filter which does not transmit as would be absorbed by the reaction product.

Process according to claim 1 which comprises efiectsaid reaction in the presence of a solvent.

Process according to claim 1 which comprises cited- 8 ing said reaction at a temperature of from to +80 C.

6. Process according to claim 1 wherein said dicarbonyl compound is a member selected from the group consisting of 7. Process according to claim 1 wherein said olefinically unsaturated compound is a member selected from the group consisting of CH =CHCL CHFCHBr, HalCH==CHAr, CHFCHalAr, ArCH=CHalAr, HalHecHalH, Hal C=CH Hal C=CHalH, Hal tibCHal 8. Process according to claim 1 wherein said carbonyl and compound is phenanthrenequinone-(9,10) and said ole-- References Cited Schonberg et al.: Chemical Reviews, vol. 40 pp. 181, 190, 193, and 196.

HOWARD s. WILLIAMS,- Primary Examiner U.S. c1. xx.

Rollo ZUl PF/ey UNITED STATES PA'JEYT OFFICE CERTIFICATE OF CUR UQCTION Patent No 3 511, 763

? ro-wso Dated Ma 12 L 1970 Invent0r(s) Carl Heinrich Krauch, Samir Farid and Dieter Hess It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, Formula I at bottom of page R3 r O l should be \C 0 I: 1 J2--C/ s! 1.1 C r C Hr-C/ -J\'; R 1?-- 0 k. 2 D

C p v n 1 olumn 7, llne 1, C should be C Ji'GNED A SEA ED- -12.197!

jsn A-t Amen:

Edmunmn Anonin flffim Iii-HIE. W, JR. L Omissions:- of Patent! 

